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N Ne-Sulfonylbis(sulfur difluoride diimide).

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95/13
10 [cl
83 [cl
I
97 [d]
IR (cm-1)
[a I
NMR
[bl
1 SO28
3080 and 3005
(C-H);
1620 (C C )
1.4725
3075, 3000,
and 2955
to 2855
4.24 (1
C--H/
s); 7.7-8.3
(1 cwallylHim);
8.8-9.7
(9 H/m)
4.95 (1 +C-H/
t); 7.7-9.8
(19 H/m)
151/760
1.4900
1401760
1.4803
(C-H);
1650 ( C = C )
3080 and 3000
(C-H);
2200 (CEC),
Raman band
3070 and 3000
(C-H);
1690 and
1660 (C=C);
1043, 1015,
949. and 886
8.6-9.3 ( 2 H /
m); 9.3-9.6
(8 H / m )
5 . 3 8 ( 2 = C - H)
and 8.41
(2 allyl-H)
as AzB2
system; 9.05
to 9.9
(8 Him)
[a] Measured on capillary film.
[b] T scale; measured in CC14 with
TM S as internal standard.
[c] Based on (21.
[dl Based on ( 5 ) .
Interestingly, (3) does not undergo a dimerizing a-elimination t o give butatriene (71, as has been observed for analogous P,@-dialkylderivatives under similar conditions [3al, but
owing to the "olefinic behabior" of the three-membered
rings [41 enters into a Fritsch-Buttenberg-Wiechell rearrangement that is characteristic of unsaturated @ substituents
(aryl[51, alkenyl, and alkynyl groups [3b1).
Experimental:
A solution of (2) (100 mmoles), prepared according to the
general procedure given in ref. [61 and purified by distillation
(spinning band column), in T H F (200ml) or THF,'ether/
light petroleum (50-70 "C) (4 : 1 : 1) (Trapp mixture 13al)
(200 ml) is treated with a solution of butyllithium (120
mmoles) in light petroleum at 20 O C under an inert gas and
the reaction mixture stirred overnight. The crude product obtained after hydrolysis and the usual working up procedure
contained ( 5 ) and (4) in 8 3 and 10% yield, respectively,
(based on (21, determined by gas chromatography) which
were obtained about 97% pure on fractional distillation over
a spinning band column, and free from impurities by preparative gas chromatography ( 6 m column, SE 30). Hydrogenation of ( 5 ) (10 mmoles) with Lindlar catalyst (0.5 g) and
quinoline 171 (0.2 g) in a shaking apparatus (70 min at 20 "C)
gave a 97% yield of (6) along with 3 % of lower boiling
products which were removed by preparative gas chromatography.
Received: January 31, 1970
[Z 150 IE]
German version: Angew. Chem. 82, 251 (1970)
__-.
[*I Prof. Dr. G. Kobrich and Dipl.-Chem. D. Merkel
Institut fiir Organische Chemie der Univerntat
69 Heidelberg, Tiergartenstrasse (Germany)
[**I This work was supported by the Deutsche Forschungsgemeinschaft, the Fonds der Chemischen Industrie, and Badische
Anilin- & Soda-Fabrik AG, Ludwigshafen.
[l] The structures of the new compounds were confirmed by
combustion analysis and spectroscopic methods.
[2] The compound was mentioned but not described by W. Y.
E . Doering and W. R . Roth, Angew. Chem. 75, 27 (1963);
Angew. Chem. internat. Edit.2,115 (1963); Tetrahedron 19,715
(1963); the trans isomer was prepared by W. LMttke [personal
communication, cf. W. Liittke and A . de Meyere, Angew. Chem.
78, 544 (1966); Angew. Chem. internat. Edit. 5, 512 (1966)l.
[3] a) G. Kobrich and W. Drischel, Tetrahedron 22,2621 (1966);
G. Kobrich, H . Heinemann, and W. Ziindorf, ibid. 23,565(1967);
G. Kobrich and H . Trapp, Chem. Ber. 99, 670, 680 (1966);
b) W. Werner, unpublished experiments.
[4] For a review, see W. A . Bernett, J. chem. Educat. 44, 17
(19 67).
244
151 For a review, see G. Kobrich, Angew. Chem. 77, 75 (1965);
Angew. Chem. internat. Edit. 4,49 (1965).
161 G. Kobrich, H . Trnpp, K . Flory, and W . Drischel, Chem.
Ber. 99, 689 (1966).
[7J H. Lindlar, Helv. chim. Acta 35, 446 (1952).
N,N'-Sulf onylbis(su1fur difluoride diimide)I1 I
By Herbert W. Roesky and Horst H . Giere[*l
Sulfamide reacts with sulfur tetrafluoride at room temperature in the presence of sodium fluoride as H F acceptor t o
give N,N'-su!fonylbis(sulfur difluoride diimide) (Z) in 22 "/,
yield.
+
H~NSO~NH
+ Z2 SF4 + F ~ S = N S O ~ N = S F Z4 H F
(1)
At higher temperatures, however, this reaction leads exclusively to formation of N-fluorosulfonylsulfur difluoride
imide FSOzN=SFz 121.
Compound ( I ) is a yellow evil-smelling liquid which loses
H F o n reaction with water. Its composition follow sfrom the
results of elemental analysis and from the mass spectrum,
which shows, in addition t o the molecular ion m!e 232 (8.7 %),
the following characteristic fragments: m / e = 167 (FSO2NSFz; 12.3%), 148 (SOzNSFz; 61.8%), 84 (NSF2; 19.7%),
83 (S02F; 18.5%), 70 (SF2; 39.473, 67 (SOF; 17.0%), 65
(NSF; 16.5%), 64 (SOz; 13.4%), 51 (SF; 10.7%), 48 (SO;
25.7 %), 46 (NS; 100.0 %), 32 (S; 6.8 "/,).
The bands in the IR spectrum (capillary) have not, as yet,
been completely identified because of the difficulties due to
coupling and superpositions. In the region of the (S=O) and
(N=S) stretching vibrations, bands occur at 1430 w, 1385 s,
1270 m, 1215 vs, and 1180 vs (cm-1). The absorptions at
820 s, 790 s, and 660 s (cm-I) have been tentatively assigned
to the (SN) and/or (SF) vibrations. The symmetry of the
molecule is confirmed by the 19F-NMR spectrum: a singlet is
observed with 8~ = -41.5 ppm (CCI3F, external) which
compares with 8~ = --40.0 ppm for FSOzNSF2.
Experimental:
Sulfur tetrafluoride (108 g, 1 mole) is condensed into a 300ml
monel cylinder cooled with liquid nitrogen and containing a
mixture of sulfamide (48 g, 0.5 mole) and sodium fluoride
(84 g, 2 moles). The cylinder is then allowed t o warm t o
room temperature and shaken for 20 hours. After removal
of gaseous components - a little SF4 and SOF2 - the reaction products are washed portionwise from the cylinder with
300ml CC14 and separated from N a F . H F by filtration
under dry nitrogen. Concentration of the filtrate followed by
distillation under vacuum affords compound ( I ) 1b.p. 49 t o
51 "Cj0.01 torr; yield 26 g (22.4x)J.
Received: December 10, 1969
[Z 152 IEI
German version: Angew. Chem. 82, 255 (1970)
[*I Univ.-Doz. Dr. H. W. Roesky and Dip1.-Chem. H. H . Giere
Anorganisch-Chemisches Institut der Universitat
34 Gottingen, Hospitalstrasse 8-9 (Germany)
[l] Sulfur-Nitrogen Compounds, Part 28. - Part 27: H . W.
Roesky, H . H . Ciere, and D . P . Babb, Inorg. Chem., in press.
[2] U . Biermnnn and 0.Gkmser, Chem. Ber. 100, 3795 (1967).
Method for Preparation of Compounds of the Type
R-(N=PX2),-N-PCl,
By Herbert W. Roesky and Ludwig F. Grimm [*I
N-Trimethylsilylaminodifluorophosphoranylidenedihalothiophosphorylamines ( I ) , prepared from the corresponding
N-trifluorophosphoranylidenedihalothiophosphorylamine
and hexamethyldisilazane [21, react with phosphorus pentaAngew. Chem. internat. Edit.
1 Vol. 9
(1970) NO. 3
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